Certain 1-(3-pyridyl)-2-phenoxy-alkanones having anti-microbial activity

ABSTRACT

Pyridinyl derivatives of formula I ##STR1## wherein R 1  to R 5  are each independently hydrogen, halogen, C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy, C 1  -C 6  haloalkoxy, cyano, C 1  -C 6  alkoxycarbonyl or phenyl, 
     R 6  and R 7  are each independently of the other hydrogen, C 1  -C 6  alkyl, C 3  -C 6  alkenyl or C 3  -C 6  alkynyl, or phenyl or benzyl, each of which is unsubstituted or substituted by halogen, C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy or C 1  -C 6  haloalkoxy, 
     R 8  is ##STR2## and R 9  is hydrogen, C 1  -C 6  alkyl, C 3  -C 6  alkenyl, C 3  -C 6  alkynyl, or benzyl which is unsubstituted or substituted by halogen, C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy or C 1  -C 6  haloalkoxy, or R 9  is an acyl radical. 
     The preparation of these compounds and the use thereof in pest control, in particular against bacteria and fungi, are described.

This application is a continuation of Ser. No. 237,659, filed on Aug. 23, 1988, now abandoned, which is a continuation of Ser. No. 912,900, filed on Sept. 26, 1986, now abandoned.

The present invention relates to pyridinyl derivatives, to the preparation thereof and to the use thereof in pest control.

The pyridinyl derivatives have the formula I ##STR3## wherein

R₁ to R₅ are each independently hydrogen, halogen, C₁ -C₆ alkyl, 1-C₆ haloalkoxy, cyano, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy, C_(C) ₁ -C₆ alkoxycarbonyl or phenyl,

R₆ and R₇ are each independently of the other hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl, or phenyl or benzyl, the aromatic ring of each of which may be unsubstituted or substituted by halogen, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy or C₁ -C₆ haloalkoxy,

R₈ is ##STR4## and

R₉ is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, or benzyl which may be unsubstituted or substituted at the ring by halogen, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy or C₁ -C₆ haloalkoxy, with the proviso that a CO group in the substituent R₈ is in the 3- or 4-position of the pyridine ring if R₁, R₂, R₄, R₅ and R₇ are simultaneously hydrogen, R₃ is methoxy and R₆ is methyl, and may also be an acyl radical R₁₀ --CO--, in which R₁₀ is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₂ -C₅ alkoxyalkyl, or C₁ -C₆ haloalkyl or is C₃ -C₆ cycloalkyl which is unsubstituted or substituted by C₁ -C₃ alkyl, or R₁₀ is one of the radicals phenyl, benzyl or phenethyl, each of which may be unsubstituted or substituted at the ring by halogen, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy or C₁ C₆ haloalkoxy.

The alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl and alkynyl radicals R₁ to R₁₀ may be straight chain or branched.

Depending on the number of indicated carbon atoms, alkyl by itself or as moiety of another substituent such as alkoxy, haloalkyl, haloalkoxy etc. shall be understood as meaning for example the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc. Halogen and halo stand for fluorine, chlorine, bromine or iodine. Haloalkyl is therefore a mono- to perhalogenated alkyl radical, e.g. CHCl₂, CH₂ F, CCl₃, CH₂ Cl, CHFCH₃, CH₂ CH₂ Br, CF₂ CF₃, C₂ Cl₅, CH₂ Br, CHBrCl etc., with CF₃ and CHF₂ being preferred. Correspondingly, the foregoing examples also apply to haloalkoxy. Alkenyl is e.g. 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl as well as chains containing several double bonds. Alkynyl is e.g. 2-propynyl, 1-butynyl, 2-butynyl, 4-pentynyl or, preferably, propargyl. Examples of C₂ -C₅ alkoxyalkyl are propoxyethyl, ethoxyethyl, ethoxymethyl, methoxymethyl.

One group of compounds comprises those compounds of formula I wherein R₁ to R₉ are as defined above, with the exception of the definition R₁₀ --CO--for the substituent R₉.

Preferred compounds of formula I are those wherein R₁ to R₅ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C_(1`-C) ₄ haloalkyl, C₁ -C₄ alkoxy, C_(C) ₁ -C₄ haloalkoxy, or one of these substituents may also be phenyl,

R₆ and R₇ are each independently of the other hydrogen, C₁ -C₆ alkyl, C₃ -C₅ alkenyl, C₃ -C₅ alkynyl, or phenyl or benzyl, each of which may be substituted at the ring by halogen, and is hydrogen, C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, benzyl or halobenzyl, or R₉ has the meaning R₁₀ --CO--, in which R₁₀ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₂ -C₅ alkoxyalkyl, C₁ -C₄ haloalkyl or is C₃ -C₆ cycloalkyl which is unsubstituted or substituted by C₁ -C₃ alkyl, or R₁₀ is one of the radicals phenyl or benzyl, each of which may be unsubstituted or substituted by a maximum of 2 substituents selected from halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy and C₁ -C₂ haloalkyl containing 1 to 3 halogen atoms, and R₈ is as defined for formula I.

Among these last-named compounds, those compounds of formula I form a group wherein R₁ to R₈ are as defined above, and

R₉ is hydrogen, C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, benzyl or halobenzyl, and R₈ is as defined for formula I (compound group Ia).

One of the important subgroups comprises those pyridinyl derivatives of formula I wherein R₈ is CO--(3-pyridinyl) or CH(OR₉)--(3-pyridinyl) and wherein

R₁ is hydrogen, methyl, ethyl or halogen,

R₂ is hydrogen,

R₃ is hydrogen, halogen, C₁ -C₃ haloalkyl, C₁ -C₃ haloalkoxy, CN or phenyl,

R₄ is hydrogen or halogen,

R₅ is hydrogen or halogen,

R₆ is C₁ -C₄ alkyl, C₃ -C₅ alkenyl, C₃ -C₅ alkynyl, or phenyl or benzyl, each of which may be substituted at the ring by halogen,

R₇ is hydrogen or C₁ -C₃ alkyl, and

R₉ is hydrogen, C₁ -C₄ alkyl, allyl, propargyl, benzyl or R₁₀ --CO--, in which R₁₀ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₁ -C₄ haloalkyl or is C₃ -C₆ cycloalkyl which is unsubstituted or substituted by methyl or ethyl.

A further important subgroup comprises those 3-pyridinyl derivatives of formula I wherein the substituents R₁ to R₈ are as defined above, and wherein R₆ is additionally hydrogen, and R₉ is hydrogen, C₁ -C₄ alkyl, allyl, propargyl or benzyl (compound group Ib).

Within compound group Ib, those compounds are preferred wherein

R₁ is hydrogen, fluorine or chlorine,

R₃ is fluorine, chlorine or bromine, CF₃, CF₃ --O-- or CHF₂ --O--,

R₂, R₄ and R₅ are hydrogen,

R₆ is hydrogen, C₂ -C₄ alkyl, allyl, propargyl, phenyl or chlorophenyl,

R₇ is hydrogen or methyl, and

R₉ is hydrogen, methyl, ethyl, isopropyl, allyl or benzyl (compound group Ic). Within compound group Ic, those representatives are particularly preferred wherein R₆ is one of the aliphatic substituents mentioned.

Another important subgroup of compounds of formula I comprises those compounds wherein

R₈ is CO--(3-pyridinyl) or CH(OR₉)--(3-pyridinyl),

R₁ is hydrogen, methyl, fluorine or chlorine,

R₃ is fluorine, chlorine or bromine, CF₃, CF₃ --O-- or CHF₂ --O--,

R₂, R₄ and R₅ are hydrogen,

R₆ is C₂ -C₄ alkyl, allyl, propargyl, phenyl or chlorophenyl,

R₇ is hydrogen or methyl, and

R₉ is the group R₁₀ --CO--, in which R₁₀ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₁ -C₂ haloalkyl or C₃ -C₅ cycloalkyl which is unsubstituted or substituted by methyl or ethyl.

A preferred subgroup of compounds of formula I comprises those compounds wherein R₁ and R₃ are chlorine and R₂, R₄, R₅ and R₇ are hydrogen, R₆ is C₁ -C₄ alkyl, and R₈ is CO--(3-pyridinyl) or CH(OR₉)--(3-pyridinyl), in which R₉ is hydrogen or R₁₀ --CO-- and R₁₀ is C₁ -C₄ alkyl, C₂ -C₅ alkoxyalkyl, C₃ -C₄ alkenyl, CF₃, cyclopropyl or methylcyclopropyl.

Among these last-named compounds, those are particularly preferred wherein R₁₀ is methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, isobutyl or tert-butyl, and R₁ to R₈ are as defined.

Among the preferred examples of compounds of formula I are, inter alia, the following representatives: ##STR5## and also the compounds 1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)butan-1-one,

1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)butan-1-ol,

1-(3-pyridinyl)-1-acetoxy-2-(2,4-dichlorophenoxy)butane,

1-(3-pyridinyl)-1-propionyloxy-2-(2,4-dichlorophenoxy)butane,

1-(3-pyridinyl)-1-methoxyacetoxy-2-(2,4-dichlorophenoxy)butane,

1-(3-pyridinyl)-2-(4-chlorophenoxy)hexan-1-one,

1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)pentan-1-ol.

The compounds of formula I wherein

R₈ is ##STR6## can be prepared e.g. by

(a) reacting an ester of formula II ##STR7## with a halide of formula III ##STR8## in the presence of a metallising agent such as Mg (e.g. in the form of a Grignard compound) or butyl lithium or

(b) allowing a compound of formula IV ##STR9## to react with a phenol of formula V ##STR10## in the presence of a base, R₁ to R₇ being as defined for formula I and Hal being halogen, preferably chlorine or bromine, and R' being C₁ -C₄ alkyl or C₃ -C₄ alkenyl, or phenyl or benzyl, each of which may be unsubstituted or substituted at the ring by alkyl, alkoxy, halogen, NO₂ or CN.

Suitable bases for process (b) are in particular tertiary amines such as trialkylamines and pyridine, and also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, as well as alkali metal alcoholates, e.g. potassium tert-butylate, or alkali metal hydrides.

To prepare compounds of formula I wherein R₆ and/or R₇ have a meaning other than hydrogen, it is sometimes advantageous, in a first reaction step, to react a compound of formula IV wherein R₆ =R₇ =hydrogen with the desired phenol of formula V and then, in a subsequent step, to introduce the desired substituent R₆ and/or R₇ in the form of a compound

    R.sub.6 -hal                                               (VIa)

    or

    R.sub.7 -hal                                               (VIb)

into the resultant compound of formula I at the activated CH₂ group, hal in formulae VIa and VIb being halogen, preferably bromine or iodine. This substitution is carried out in the presence of strong bases such as sodium methylate or, preferably, potassium tert-butylate.

Process (a) is carried out either in the absence or, preferably, in the presence of a solvent or diluent and at a temperature in the range from -130° to +50° C., preferably from -130° C. to +20° C.

Process (b) is also preferably carried out in a solvent in the temperature range from -50° to +150° C., preferably from 0° to +120° C. Suitable solvents or diluents are inert representatives which do not contain hydroxyl groups, e.g. ethers and ethereal compounds such as diethyl ether, diisopropyl ether, dioxane, 1,2-dimethoxyethane and tetrahydrofuran; amides such as N,N-dialkylated carboxamides of the type dimethylformamide; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform and chlorobenzene; nitriles such as acetonitrile; dimethyl sulfoxide and ketones such as acetone or methyl ethyl ketone.

The ketones of formula I prepared by the above processes can be converted by known methods of hydrogenation and, if desired, by subsequent reaction with a compound of formula VII

    R"Hal                                                      (VII)

into compounds of formula I wherein

R₈ is ##STR11## and

R₉ is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, or benzyl which may be substituted at the ring by halogen, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy or C₁ -C₆ haloalkoxy.

R" in formula VII is C₁ -C₆ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl, or benzyl which is unsubstituted or substituted at the nucleus by halogen, C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, C₁ -C₆ alkoxy or C₁ -C₆ haloalkoxy.

In order to obtain acyl compounds, compounds of formula I wherein R₉ is hydrogen can be reacted with a corresponding carboxylic acid R₁₀ --COOH or with an acid halide (preferably acid chloride or bromide) or acid anhydride thereof. The temperature should be in the range from -20° C. to +80° C. and OH-free solvents or diluents may be used (see above).

Compounds of formulae II to VII are known or they can be prepared by known processes.

If they contain an asymmetric carbon atom, compounds of formula I may be obtained in two enantiomeric forms. In general, when preparing these substances a mixture of both enantiomers forms, which mixture can be resolved in known manner into the pure optical antipodes. Compounds of formula I with two centres of assymetry are also obtained as mixtures of diastereoisomers, which mixtures can be resolved by physical methods. The present invention relates to all pure enantiomers and diastereoisomers and mixtures thereof with one another.

The compounds of formula I of this invention have, for practical application purposes, a very advantageous microbicidal spectrum against phytopathogenic fungi and bacteria. Compounds of formula I have very advantageous curative, systemic and, in particular, preventive properties, and can be used for protecting numerous cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms.

The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g. the genera Hemileia, Rhizocotonia, Puccinia); and, in particular, against the class of the Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula). In addition, the compounds of formula I have a systemic action. They can also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic fungi which occur in the soil. Some of the compounds of formula I also exhibit plant regulating activity and can be used at higher rates of application for curbing excessive vegetative growth in crops of cultivated plants.

The invention also relates to microbicidal compositions as well as to the use of the compounds of formula I for controlling phytopathogenic microorganisms, in particular phytopathogenic fungi, or for protecting plants from attack by said microorganisms.

The invention further embraces the preparation of agrochemical compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of formula I or the novel compositions.

Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons), fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites).

The structurally closest compound known from the art is 2-(4-methoxyphenoxy)-1-(2-pyridinyl)-1-propanone which is disclosed in German Offenlegungsschrift No. 29 09 754 as an intermediate for the preparation of pharmaceutically active benzofuran derivatives. This compound is not known to have microbicidal activity.

The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 150 g to 600 g a.i./ha.

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethylene glycol monomethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils or soybean oil; or water.

Solid carriers which can be used e.g. for dusts and dispersible powders are calcite, talcum, kaolin, montmorillonite or attapulgite, highly dispersed silicic acid or absorbent polymers. Suitable granulated adsorptive carriers are pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are e.g. calcite or dolomite. Pregranulated materials may also be used.

Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

The surfactants customarily employed in the art of formulation are described e.g. in:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., 1980;

Sisley and Wood, "Encylopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1980.

Particularly advantageous application promoting adjuvants are also natural or synthetic phospholipids of the series of the cephalins and lecithins, e.g. phospatidyl ethanolamine, phosphatidyl serine, phosphatidyl glycerol and lysolecithin.

The agrochemical compositions usually contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of formula I, 99.9 to 1%, preferably 99.9 to 5%, of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

EXAMPLE 1: PREPARATORY EXAMPLES FOR COMPOUNDS OF FORMULA I EXAMPLE 1.1: PREPARATION OF 2-(2,4-DICHLOROPHENOXY)-1-(3-PYRIDINYL)-1-ETHANONE

140.2 g of 93% 2,4-dichlorophenyl and 232 g of potassium carbonate are added to 1000 ml of acetone. After brief heating to boiling temperature, the reaction mixture is cooled to 0° C., and a total of 224.8 g of 3-(bromoacetyl)pyridine hydrobromide are added in portions over one hour. The reaction mixture is stirred for 15 hours at 0° C. to 5° C. and then for 6 hours at 20° C. After filtration and concentration by evaporation of the reaction mixture, the crude product is recrystallised from methanol.

Compound 1 of the formula ##STR12## with a melting point of 118°-119° C. is obtained.

EXAMPLE 1.2: PREPARATION OF 2-(2,4-DICHLOROPHENOXY)-1-(3-PYRIDINYL)-1-PROPANONE

With cooling, 17.38 g of 2,4-dichlorophenoxyacetyl-3-pyridine are added to 8.05 g of potassium tert-butylate in 140 ml of dry tetrahydrofuran, the temperature of the solution rising to 35° C. 19.7 g of methyl iodide are added dropwise at 20° C. to the solution. After stirring for 1 hour at 45° C., the crude product is isolated by filtration and then purified by column chromatography (silica gel; eluant a 1:1.5 mixture of ethyl acetate and hexane).

Compound 2 of the formula ##STR13## with a refractive index n_(D) ³²° of 1.5884 is obtained.

EXAMPLE 1.3: PREPARATION OF 1-(3-PYRIDINYL)-2-METHYL-2-(4-CHLOROPHENOXY)PROPANONE

Under an atmosphere of argon, 12 ml of butyl lithium in 1.6 ml of hexane are dissolved in 50 ml of ether. 2.6 g of 3-bromopyridine are rapidly added at -70° C. After stirring for 30 minutes at -70° C., 3.8 g of ethyl 2-methyl-2-(4-chlorophenoxy)propionate are added to the suspension. After stirring for 30 minutes at -70° C. and for 1 hour at 20° C., 20 ml of saturated ammonium sulfate solution and 5 ml of saturated soda solution are added to the reaction mixture. The mixture is then dried over Na₂ SO₄, concentrated by evaporation and chromatographed (silica gel; eluant: a 1:2 mixture of ethyl acetate and hexane).

Compound 3 of the formula ##STR14## with a melting point of 44°-47° C. is obtained.

EXAMPLE 1.4: PREPARATION OF 1-(3-PYRIDINYL)-2-(2,4-DICHLOROPHENOXY)BUTAN-1-OL

1.8 g of NaBH₄ are added in portions to 11.16 g of 2-(2,4-dichlorophenoxy)butyryl-3-pyridine in 105 ml of methanol. After stirring for 1.5 hours at 40° C., the solution is concentrated by evaporation and taken up in ethyl acetate, and the resultant solution is washed with water and brine, dried and concentrated by evaporation.

The crude product crystallises from a 1:1.5 mixture of ethyl acetate and hexane, affording compound 4 of the formula ##STR15## with a melting point of 118°-120° C. (essentially in the form of a pure diastereoisomer).

EXAMPLE 1.5: PREPARATION OF 1-(3-PYRIDINYL)-1-METHOXY-2-(2,4-DICHLOROPHENOXY)BUTANE

4.53 g of 1-(3-pyridyl)-2-(2,4-dichlorophenoxy)butan-1-ol (essentially in the form of a pure diastereoisomer) in 15 ml of tetrahydrofuran are added dropwise to a suspension of 0.8 g of NaH (50% oil dispersion, washed in toluene) in 14 ml of tetrahydrofuran. When the evolution of hydrogen ceases, 10 ml of methyl iodide are added. After 2 hours at 20° C., the ensuing reaction is complete. The reaction mixture is concentrated by evaporation and diluted with water, and the aqueous solution is extracted with ether. The organic phase is separated, washed with water and brine, dried over Na₂ SO₄, hardened (active carbon) and concentrated by evaporation. The crude product is distilled at 145°-150° C./10⁻² mbar, affording compound 5 of the formula ##STR16## with a refractive index n_(D) ³⁰° of 1.5586 (essentially in the form of a pure diastereoisomer).

EXAMPLE 1.6: PREPARATION OF 1-(3-PYRIDINYL)-2-(2,4-DICHLOROPHENOXY)-1-BUTANONE OF THE FORMULA ##STR17## With slight cooling, 9.2 g of 1-(3-pyridyl)-2-(2,4-dichlorophenoxy)-1-ethanone are slowly added to a solution of 4.15 g of potassium tert-butylate in 45 ml of tetrahydrofuran. 2.9 ml of ethyl iodide are added to the resultant dark red solution. After stirring for 1 hour at room temperature and for 2 hours at 40° C., the solution is concentrated and filtered, and the residue is purified through 450 g of silica gel (eluant: a 1:1.5 mixture of ethyl acetate and hexane), affording 3.4 g of final product with a refractive index n_(D) ³⁰° of 1.5868. EXAMPLE 1.7: PREPARATION OF 1-ACETOXY-1-(3-PYRIDINYL)-2-(2,4-DICHLOROPHENOXY)BUTANE OF THE FORMULA ##STR18## 1.8 ml of acetic anhydride are added to 5.2 g of 1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)butan-1-ol (Example 1.4) in 25 ml of pyridine. After stirring at room temperature overnight, the solution is concentrated by evaporation and taken up in ethyl acetate. The resultant solution is washed with water and saturated NaCl solution, dried over Na₂ SO₄ and concentrated by evaporation, affording 5.0 g of product with a refractive index n_(D) ³⁰° of 1.5521.

Instead of acetic anhydride, it is also possible to employ 1.2 ml of acetyl chloride or acetyl bromide which, dissolved in 5 ml of glacial acetic acid, are added dropwise at about 40° C. to a solution of the same amount of starting material in 25 ml of glacial acetic acid. The reaction mixture is then stirred for 1 hour and worked up.

The following compounds of formula I are also prepared in corresponding manner:

    __________________________________________________________________________      ##STR19##                                  (I)                                                                     Physical                                  Comp.                                                                              R.sub.1                                                                          R.sub.2                                                                           R.sub.3                                                                            R.sub.4                                                                          R.sub.5                                                                          R.sub.6                                                                             R.sub.7                                                                           R.sub.8     data                                      __________________________________________________________________________      6  H H  Cl  H H H    H                                                                                  ##STR20##  m.p.: 107-108° C.                   7  H H  Br  H H H    H                                                                                  ##STR21##  m.p.: 118-119° C.                   8  H H  F   H H H    H                                                                                  ##STR22##  m.p.: 109-111° C.                   9  H H  CH.sub.3                                                                           H H H    H                                                                                  ##STR23##  m.p.: 96-97° C.                    10  H Cl H   Cl                                                                               H H    H                                                                                  ##STR24##  m.p.: 102-104° C.                  11  Cl                                                                               H  H   H H H    H                                                                                  ##STR25##  m.p.: 86-88° C.                    12  H H  CF.sub.3                                                                           H H H    H                                                                                  ##STR26##  m.p.: 127-129° C.                  13  H Cl H   H H H    H                                                                                  ##STR27##  m.p.: 91-92° C.                    14  H CF.sub.3                                                                          H   H H H    H                                                                                  ##STR28##  m.p.: 65-67° C.                    15  H CH.sub.3                                                                          Cl  H H H    H                                                                                  ##STR29##  m.p.: 93-95° C.                    16  H H  OCH.sub.3                                                                          H H H    H                                                                                  ##STR30##  m.p.: 85-87° C.                    17  Cl                                                                               H  H   H H CH.sub.3                                                                            H                                                                                  ##STR31##  n.sub.D.sup.30°  = 1.5821          18  H Cl H   H H CH.sub.3                                                                            H                                                                                  ##STR32##  m.p.: 59-61° C.                    19  H H  Cl  H H CH.sub.3                                                                            H                                                                                  ##STR33##  m.p.: 76-77° C.                    20  H H  CF.sub.3                                                                           H H CH.sub.3                                                                            H                                                                                  ##STR34##  n.sub.D.sup.30°  = 1.5220          21  H CF.sub.3                                                                          H   H H CH.sub.3                                                                            H                                                                                  ##STR35##  n.sub.D.sup.+°  = 1.5212           22  H H  F   H H CH.sub.3                                                                            H                                                                                  ##STR36##  m.p.: 71-73° C.                    23    H  Br  H H CH.sub.3                                                                            H                                                                                  ##STR37##  m.p.: 69-71° C.                    24  H H  CH.sub.3                                                                           H H CH.sub.3                                                                            H                                                                                  ##STR38##  m.p.: 91-93° C.                    25  H CH.sub.3                                                                          Cl  H H CH.sub.3                                                                            H                                                                                  ##STR39##  m.p.: 59-61° C.                    26  H Cl H   Cl                                                                               H CH.sub.3                                                                            H                                                                                  ##STR40##  n.sub.D.sup.30°  = 1.5869          27  Cl                                                                               H  Cl  H H C.sub.4 H.sub.9 (t)                                                                 H                                                                                  ##STR41##  n.sub.D.sup.40°  = 1.5601          28  H H  OCH.sub.3                                                                          H H CH.sub.3                                                                            H                                                                                  ##STR42##  n.sub.D.sup.30°  = 1.5701          29  Cl                                                                               H  Cl  H H C.sub.2 H.sub.5                                                                     H                                                                                  ##STR43##  b.p.: 152-154/ 10.sup.-2 mbar             30  Cl                                                                               H  Cl  H H C.sub.4 H.sub.9 (n)                                                                 H                                                                                  ##STR44##  n.sub.D.sup.40°  = 1.5600          31  Cl                                                                               H  Cl  H H C.sub.3 H.sub.7 (n)                                                                 H                                                                                  ##STR45##  n.sub.D.sup.30°  = 1.5662          32  H H  Cl  H H C.sub.2 H.sub.5                                                                     H                                                                                  ##STR46##  n.sub.D.sup.30°  = 1.5755          33  Cl                                                                               H  Cl  H H CH.sub.3                                                                            CH.sub.3                                                                           ##STR47##  n.sub.D.sup.30°  = 1.5753          34  Cl                                                                               H  Cl  H H C.sub.2 H.sub.5                                                                     CH.sub.3                                                                           ##STR48##  n.sub.D.sup.30 ° = 1.5722          35  Cl                                                                               H  Cl  H H H    H                                                                                  ##STR49##  m.p.: 125-126° C.                  36  Cl                                                                               H  Cl  H H C.sub.2 H.sub.5                                                                     H                                                                                  ##STR50##  n.sub.D.sup.30°  = 1.5770          37  Cl                                                                               H  Cl  H H C.sub.2 H.sub.5                                                                     H                                                                                  ##STR51##  n.sub.D.sup.30°  = 1.5740          38  Cl                                                                               H  Cl  H H C.sub.3 H.sub.7 (n)                                                                 H                                                                                  ##STR52##  n.sub.D.sup.30°  = 1.5662          39  Cl                                                                               H  Cl  H H C.sub.3 H.sub.7 (n)                                                                 H                                                                                  ##STR53##                                            40  Cl                                                                               H  Cl  H H C.sub.6 H.sub.5                                                                     H                                                                                  ##STR54##  m.p. 105-107° C.                   41  Cl                                                                               H  H   H H C.sub.3 H.sub.7 (i)                                                                 H                                                                                  ##STR55##  n.sub.D.sup.30°  = 1.5705          __________________________________________________________________________

The following compounds of the formula

    ______________________________________                                          ##STR56##                                                                     can also be prepared in the same manner or by the methods                      indicated above (n = index 1, 2 or 3);                                         Me = methyl, Et = ethyl, nPr = n-propyl, iPr = isopropyl                                                         Physical                                     Comp. R.sub.n   R.sub.6     R.sub.7                                                                              data                                         ______________________________________                                         42    4-Cl      iPr         H                                                  43    4-Cl      nPr         H     n.sub.D.sup.30 = 1.5628                      44    4-Cl      n-butyl     H     n.sub.D.sup.40 = 1.5519                      45    4-Cl      Et          Me                                                 46    2-F, 4-Cl Et          H                                                  47    2-F, 4-Cl nPr         H                                                  48    2-F, 4-Cl iPr         H                                                  49    4-F       Et          H     n.sub.D.sup.30 = 1.5468                      50    4-F       nPr         H                                                  51    4-F       iPr         H                                                  52    4-Br      Et          H     n.sub.D.sup.40 = 1.5809                      53    4-Br      Et          Me                                                 54    4-Br      nPr         H                                                  55    4-Br      iPr         H                                                  56    4-Br      n-butyl     H                                                  57    4-phenyl  Et          H     n.sub.D.sup.40 = 1.6083                      58    4-phenyl  nPr         H                                                  59    4-phenyl  iPr         H                                                  60    4-OCH.sub.3                                                                              nPr         H                                                  61    H         Et          H                                                  62    H         nPr         H                                                  63    4-tert-butyl                                                                             nPr         H                                                  64    4-methoxy Et          H                                                  65    4-methoxy iPr         H                                                  66    4-CF.sub.3                                                                               iPr         H                                                  67    3-CF.sub.3                                                                               nPr         H                                                  68    4-COOCH.sub.3                                                                            Et          H                                                  69    4-CF.sub.3 O                                                                             nPr         H                                                  70    4-CF.sub.3 O                                                                             iPr         H                                                  71    4-CF.sub.3 O                                                                             Et          H     n.sub.D.sup.40 = 1.5021                      72    4-CHF.sub.2 O                                                                            Et          H                                                  73    4-CHF.sub.2 O                                                                            nPr         H                                                  74    4-CHF.sub.2 O                                                                            iPr         H                                                  75    4-CN      Et          H                                                  76    2,4-diCl  allyl       H                                                  77    2,4-diCl  propargyl   H                                                  78    3,4-diCl  nPr         H     n.sub.D.sup.35 = 1.5713                      79    2,3-diCl  nPr         H                                                  80    3-Cl      Et          H                                                  81    4-CHF.sub.2 O                                                                            Me          Me                                                 82    2,4-diCl  benzyl      H                                                  83    4-Cl      benzyl      H                                                  84    2-Cl, 4-F Et          H     n.sub.D.sup.40 = 1.5514                      85    2-Cl, 4-Br                                                                               iPr         H                                                  86    2,4-diF.sub.2                                                                            n-butyl     H                                                  87    4-CF.sub.3                                                                               Et          H     n.sub.D.sup.40 = 1.5125                      88    2,4-diCl  C.sub.6 H.sub.4 Cl(4)                                                                      H     m.p. 94-96° C.                        89    4-Cl      C.sub.6 H.sub.5                                                                            H     m.p. 111-113° C.                      90    4-Cl      C.sub.6 H.sub.4 Cl(4)                                                                      H     m.p. 86-88° C.                        91    4-Cl      sec-butyl   H     n.sub.D.sup.35 = 1.5559                      92    2,4-diCl  sec-butyl   H     n.sub.D.sup.35 = 1.5652                      93    4-Cl      C.sub.6 H.sub.4 Cl(2)                                                                      H     m.p. 95-97° C.                        94    2,4-diCl  C.sub.6 H.sub.4 Cl(2)                                                                      H     highly viscous                               95    2,4-diCl  C.sub.6 H.sub.3 diCl(2,6)                                                                  H     highly viscous                               96    2,4,6-triCl                                                                              Et          H     n.sub.D.sup.35 = 1.5710                      97    2-CH.sub.3,4-Cl                                                                          Et          H     n.sub.D.sup.35 = 1.5623                      ______________________________________                                    

The following compounds of the formula

    ______________________________________                                          ##STR57##                                                                     can also be prepared by the procedure of Example 1.4                           or 1.5 or by one of the methods indicated above                                (n = index, 1, 2, or 3;                                                        Me = methyl, Et = ethyl, nPr = n-Propyl, iPr = isopropyl)                      Comp. R.sub.n   R.sub.6 R.sub.7                                                                             R.sub.9                                                                               Physical data                              ______________________________________                                         2.1   4-Cl      Et      H    H                                                 2.2   4-Cl      Et      H    Me                                                2.3   2,4-diCl  Et      H    allyl                                             2.4   2,4-diCl  Et      H    pro-                                                                           pargyl                                            2.5   2,4-diCl  nPr     H    H      n.sub.D.sup.40 = 1.5678                    2.6   2,4-diCl  iPr     H    H      n.sub.D.sup.50 = 1.5620                    2.7   2,4-diCl  nPr     H    Me     n.sub.D.sup.40 = 1.5491                    2.8   2,4-diCl  iPr     H    Me     n.sub.D.sup.30  = 1.5528                   2.9   2,4-diCl  n-butyl H    H      n.sub.D.sup.40 = 1.5531                    2.10  2,4-diCl  n-butyl H    Me     n.sub.D.sup.30 = 1.5470                    2.11  2-Cl, 4-F Et      H    H      n.sub.D.sup.40 = 1.5528                    2.12  2-Cl, 4-F Et      H    Me                                                2.13  4-F       nPr     H    Me                                                2.14  4-Br      n-butyl H    Me                                                2.15  2,6-diCl  Me      Me   H                                                 2.16  2,4-diCl  Me      Me   Me                                                2.17  4-OCH.sub.3                                                                              Et      H    H                                                 2.18  4-CF.sub.3                                                                               nPr     H    H                                                 2.19  4-CF.sub.3                                                                               nPr     H    Me                                                2.20  4-CF.sub.3 O                                                                             Et      H    H                                                 2.21  4-CF.sub.3 O                                                                             Et      H    Et                                                2.22  4-CN      Et      H    Me                                                2.23  2,4-diF   n-butyl H    Me                                                2.24  3,4-diCl  Et      H    H                                                 2.25  2,3-diCl  nPr     H    H                                                 2.26  2,3-diCl  nPr     H    Me                                                2.27  4-Me      Et      H    Me                                                2.28  2,4-diCl  phenyl  H    H                                                 2.29  2,4-diCl  phenyl  H    Me                                                2.30  2,4-diCl  Me      H    H      m.p. 88-100° C.                     2.31  2,4-diCl  Me      H    Me     n.sub.D.sup.31 = 1.5642                    2.32  2,4-diCl  H       H    H      m.p. 117-119° C.                    2.33  2,4-diCl  H       H    Me     n.sub.D.sup.31 = 1.5716                    2.34  2,4,6-triCl                                                                              Et      H    H      m.p. 118-121° C.                    2.35  2-CH.sub.3,4-Cl                                                                          Et      H    H      m.p. 69-72° C.                      ______________________________________                                    

The following acyl compounds are also prepared by the procedure of Example 1.7

    ______________________________________                                          ##STR58##                                                                                                      Physical                                      Comp. R.sup.10          R.sup.6  data                                          ______________________________________                                         3.1   CH.sub.3          C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5521                       3.2   CH.sub.2 CH.sub.3 C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5470                       3.3   CH.sub.2 CH.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5398                       3.4   CF.sub.3          C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5188                       3.5   C(CH.sub.3).sub.3 C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5350                       3.6                                                                                   ##STR59##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5783                       3.7                                                                                   ##STR60##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5774                       3.8                                                                                   ##STR61##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5831                       3.9                                                                                   ##STR62##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5408                       3.10                                                                                  ##STR63##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.35 = 1.5824                       3.11                                                                                  ##STR64##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.35 = 1.5882                       3.12                                                                                  ##STR65##        C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5781                       3.13  CH.sub.3          C.sub.4 H.sub.9 (n)                                                                     n.sub.D.sup.30 = 1.5395                       3.14  CH.sub.2 OCH.sub.3                                                                               C.sub.2 H.sub.5                                                                         n.sub.D.sup.30 = 1.5471                       3.15  CH.sub.2 OCH.sub.3                                                                               C.sub.4 H.sub.9 (n)                                                                     n.sub.D.sup.30 = 1.5400                       3.16                                                                                  ##STR66##        C.sub.4 H.sub.9 (n)                                                                     n.sub.D.sup.30 = 1.5702                       3.17                                                                                  ##STR67##        C.sub.4 H.sub.9 (n)                                                                     n.sub.D.sup.30 = 1.5739                       3.18                                                                                  ##STR68##        C.sub.4 H.sub.9 (n)                                                                     n.sub.D.sup.30 = 1.5673                       3.19                                                                                  ##STR69##        C.sub.4 H.sub.9 (n)                                                                     n.sub.D.sup.30 = 1.5396                       ______________________________________                                    

as well as the following acyl compounds

    __________________________________________________________________________      ##STR70##                                                                     Comp.                                                                               R.sup.10  R.sup.6                                                                              T      Physical data                                      __________________________________________________________________________     4.1  C.sub.3 H.sub.7 (iso)                                                                    C.sub.2 H.sub.5                                                                      2,4-di-Cl                                                                             n.sub.D.sup.30 = 1.5394                            4.2                                                                                  ##STR71##                                                                               C.sub.2 H.sub.5                                                                      2,4-di-Cl                                                                             n.sub.D.sup.30 = 1.5559                            4.3  CH.sub.2 CH.sub.2 CH.sub.3                                                               C.sub.4 H.sub.9 (n)                                                                  2,4-di-Cl                                                 4.4  CH.sub.2 CH.sub.3                                                                        C.sub.4 H.sub.9 (n)                                                                  2,4-di-Cl                                                                             n.sub.D.sup.30 = 1.5388                            4.5  CH.sub.3  C.sub.2 H.sub.5                                                                      4-Cl                                                      4.6  CH.sub.3  C.sub.4 H.sub.9 (n)                                                                  4-Cl                                                      4.7  CH.sub.3  C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.8  CH.sub.2 CH.sub.3                                                                        C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.9  CH.sub.2 CH.sub.2 CH.sub. 3                                                              C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.10 C.sub.3 H.sub.7 (iso)                                                                    C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.11 CH.sub.2 CH.sub.3                                                                        C.sub.3 H.sub.7 (n)                                                                  4-Cl                                                      4.12 CH.sub.2 CH.sub.3                                                                        C.sub.3 H.sub.7 (iso)                                                                2,4-di-Cl                                                                             n.sub.D.sup.50 = 1.5350                            4.13 CH.sub.3  C.sub.3 H.sub.7 (iso)                                                                2,4-di-Cl                                                                             m.p. 116-117° C.                            4.14 C.sub.6 H.sub.4 Cl(4)                                                                    C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.15 C.sub.6 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.16 C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                           C.sub.3 H.sub.7 (n)                                                                  2,4-di-Cl                                                 4.17 C(C.sub.2 H.sub.5)CH.sub.2                                                               C.sub.2 H.sub.5                                                                      2,4-di-Cl                                                 4.18 C(CH.sub.3).sub.3                                                                        C.sub.3 H.sub.7 iso                                                                  2,4-di-Cl                                                                             n.sub.D.sup.50 = 1.5250                            4.19 C.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 iso                                                                  2,4-di-Cl                                                 4.20 C.sub.3 H.sub.7 iso                                                                      C.sub.3 H.sub.7 iso                                                                  2,4-di-Cl                                                                             n.sub.D.sup.50 = 1.5294                            4.21                                                                                 ##STR72##                                                                               C.sub.3 H.sub.7 iso                                                                  2,4-di-Cl                                                                             n.sub.D.sup.50 = 1.5425                            4.22                                                                                 ##STR73##                                                                               C.sub.4 H.sub.9 n                                                                    2,4-di-Cl                                                                             n.sub.D.sup.30 = 1.5468                            4.23 C.sub.3 H.sub.7 iso                                                                      C.sub.4 H.sub.9 n                                                                    2,4-di-Cl                                                                             n.sub.D.sup.30 = 1.5312                            4.24 C(CH.sub.3).sub.3                                                                        C.sub.4 H.sub.9 n                                                                    2,4-di-Cl                                                                             n.sub.D.sup.30 = 1.5284                            4.25 CH.sub.3  C.sub.2 H.sub.5                                                                      2-CH.sub.3, 4-Cl                                                                      n.sub.D.sup.30 = 1.5484                            4.26 CH.sub.3  C.sub.2 H.sub.5                                                                      2,4,6-tri-Cl                                                                          n.sub.D.sup.30 = 1.5603                            4.27 CH.sub.3  C.sub.2 H.sub.5                                                                      2-Cl, 4-F                                                                             n.sub.D.sup.30 = 1.5496                            4.28 CF.sub.3  C.sub.3 H.sub.7 iso                                                                  2,4-di-Cl                                                 4.29                                                                                 ##STR74##                                                                               C.sub.3 H.sub.7 iso                                                                  2,4-di-Cl                                                 __________________________________________________________________________

EXAMPLE 2: FORMULATION EXAMPLES FOR ACTIVE INGREDIENTS OF FORMULA I ACCORDING TO THE PREPARATORY EXAMPLES OR TABLES 1 TO 4

    ______________________________________                                         (throughout, percentages are by weight)                                        2.1. Emulsifiable concentrates                                                                      (a)    (b)    (c)  (d)                                    ______________________________________                                         compound according to the Preparatory                                                               10%    25%    40%  50%                                    Examples or Tables 1 to 4                                                      calcium dodecylbenzenesulfonate                                                                     --      5%     8%   6%                                    castor oil polyethylene glycol                                                                      --      5%    --   --                                     ether (36 moles of ethylene oxide)                                             tributylphenol polyethylene glycol                                                                  --     --     12%   4%                                    ether (30 moles of ethylene oxide)                                             castor oil thioxilate                                                                               25%    --     --   --                                     cyclohexanone        --     --     15%  20%                                    butanol              15%    --     --   --                                     xylene mixture       --     65%    25%  20%                                    ethyl acetate        50%    --     --   --                                     ______________________________________                                    

Emulsions of any required concentration can be produced from such concentrates by dilution with water.

    ______________________________________                                         2.2. Solutions          (a)    (b)                                             ______________________________________                                         compound according to the Preparatory                                                                  10%     5%                                             Examples or Tables 1 to 4                                                      ethylene glycol monomethyl ether                                                                       --     --                                              polyethylene glycol (mol. wt. 400)                                                                     70%    --                                              N-methyl-2-pyrrolidone  20%    --                                              expoxidised coconut oil --      1%                                             ligroin (boiling range 160-190° C.)                                                             --     94%                                             ______________________________________                                    

These solutions are suitable for application in the form of microdrops.

    ______________________________________                                         2.3. Wettable powders                                                                               (a)     (b)     (c)                                       ______________________________________                                         compound according to the Preparatory                                                               25%     50%     75%                                       Examples or Tables 1 to 4                                                      sodium lignosulfonate                                                                                5%      5%     --                                        sodium laurylsulfate  3%     --       5%                                       sodium diisobutylnaphthalenesulfonate                                                               --       6%     10%                                       octylphenol polyethylene glycol ether                                                               --       2%     --                                        (7-8 moles of ethylene oxide)                                                  highly dispersed silicic acid                                                                        5%     10%     10%                                       kaolin               62%     27%     --                                        ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

    ______________________________________                                         2.4. Suspension concentrate                                                    ______________________________________                                         compound according to the Preparatory                                                                  40%                                                    Examples or Tables 1 to 4                                                      ethylene glycol         10%                                                    nonylphenol polyethylene glycol ether                                                                   6%                                                    (15 moles of ethylene oxide)                                                   sodium lignosulfonate   10%                                                    carboxymethylcellulose   1%                                                    37% aqueous formaldehyde solution                                                                      0.2%                                                   silicone oil in the form of a 75%                                                                      0.8%                                                   aqueous emulsion                                                               water                   32%                                                    ______________________________________                                    

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

EXAMPLE 3: BIOLOGICAL EXAMPLES EXAMPLE 3.1.: ACTION AGAINST PUCCINIA GRAMINIS ON WHEAT a) Residual-Protective Action

Wheat plants are treated 6 days after sowing with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100% relative humidity and about 20° C. and then stood in a greenhouse at about 22° C. Evaluation of rust pustule development is made 12 days after infection.

b) Systemic Action

Wheat plants are treated 5 days after sowing with a spray mixture (0.006% active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The plants are then incubated for 48 hours at 95-100% relative humidity and about 20° C. and then stood in a greenhouse at about 22° C. Evaluation of rust pustule development is made 12 days after infection.

Compounds of the Tables exhibit very good activity against Puccinia fungi. Puccinia attack is 100% on untreated and infected control plants. The compounds 2-7, 19, 29, 30, 2.5-2.8, 2.11, 2.34, 3.1, 3.2, 3.14, 4.1, 4.2, 4.4, 4.22-4.27 inhibit Puccinia attack to 10% or less.

EXAMPLE 3.2.: ACTION AGAINST CERCOSPORA ARACHIDICOLA ON GROUNDNUT PLANTS Residual Protective Action

Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.006% active ingredient) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21° C. and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection and is based on the number and size of the specks.

Compared with untreated and infected control plants (number and size of the specks=100%), Cercospora attack on groundnut plants treated with compounds of the Tables is substantially reduced. The compounds 2, 19, 29, 2.5, 2.6, 2.7, 2.8, 2.11, 3.1, 3.2, 4.1, 4.2, 4.4, 4.25 and others inhibit the occurrence of specks almost completely (0 to 10%) in the above test.

EXAMPLE 3.3.: ACTION AGAINST ERYSIPHE GRAMINIS ON BARLEY a) Residual Protective Action

Barley plants about 8 cm in height are sprayed with a spray mixture (0.002% active ingredient) prepared from a wettable powder formulation of the test compound. The treated plants are dusted with conidia of the fungus after 3 to 4 hours. The infected barley plants are stood in a greenhouse at about 22° C. The fungus attack is evaluated after 10 days.

b) Systemic Action

A spray mixture (0.0006% active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound is poured onto barley plants about 8 cm in height. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a conidia suspension of the fungus. The infected barley plants are then stood in a greenhouse at about 22° C. and evaluation of infestation is made after 10 days.

Compounds of formula I exhibit good activity against Erysiphe fungi. Erysiphe attack is 100% on untreated and infected control plants. The compounds 2, 3, 5, 8, 19, 20, 23, 27, 29, 30, 96, 97, 2.5-2.11, 2.30-2.35, 3.1-3.3, 3.11, 3.13-3.15, 3.19, 4.1, 4.2, 4.4, 4.22-4.23 and others inhibit fungus attack on barley to 0 to 5%.

EXAMPLE 3.4.: RESIDUAL-PROTECTIVE ACTION AGAINST VENTURIA INAEQUALIS ON APPLE SHOOTS

Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006% active ingredient) prepared from a wettable powder formulation of the test compound. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100% relative humidity and stood in a greenhouse for a further 10 days at 20°-24° C. Evaluation of scab infestation is made 15 days after infection. Compounds of formula I inhibit attack to less than 10%, e.g. compounds 29, 30, 3.1, 3.2 and others. Venturia attack on untreated and infected shoots is 100%.

EXAMPLE 3.5.: ACTION AGAINST BOTRYTIS CINEREA ON BEANS Residual Protective Action

Bean plants about 10 cm in height are sprayed with a spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100% relative humidity and 21° C. and then evaluated for fungus attack. Many of the compounds of the Tables inhibit fungus infection very strongly. At a concentration of 0.02% the compounds of formula I are completely effective. Attack is 10% or less, e.g. after treatment with compounds 3, 5, 11, 29, 30, 2.5-2.8, 3.1, 3.2, 4.1, 4.4, 4.23. Botrytris attack on untreated and infected bean plants is 100%.

EXAMPLE 3.6.: ACTION AGAINST PYRICULARIA ORYZAE ON RICE PLANTS Residual Protective Action

After a cultivation period of 2 weeks, rice plants are sprayed with a spray mixture (0.002% active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a conidia suspension of the fungus. Evaluation of fungus attack is made after incubation for 5 days at 95-100% relative humidity and 24° C.

In comparison with untreated control plants (100% attack), fungus attack is less than 20% (in some cases there is no fungus attack) on rice plants which have been treated with a spray mixture containing as active ingredient one of the compounds of formula I. 

We claim:
 1. A pyridinyl carbonyl compound of formula I ##STR75## wherein R₁ and R₃ are each independently hydrogen, halogen, C₁ -C₄ alkyl or trifluoromethyl;R₆ and R₇ are each independently hydrogen or C₁ -C₄ alkyl.
 2. A compound of formula I according to claim 1 whereinR₁ and R₃ are each independently hydrogen, chlorine, methyl or trifluoromethyl; R₆ is hydrogen; R₇ is C₁ -C₄ alkyl.
 3. A compound of formula I according to claim 2 whereinR₁ and R₃ are chlorine; R₆ is hydrogen; R₇ is C₁ -C₄ alkyl.
 4. A compound according to claim 1 selected from the group consisting of1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)butan-1-one, 1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)-isopentan-1-one, 1-(3-pyridinyl)-2-(4-chlorophenoxy)hexan-1-one, 1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)-pentan-1-one, and 1-(3-pyridinyl)-2-(2,4-dichlorophenoxy)-hexan-1-one.
 5. A composition for controlling microorganisms or for preventing attack by said microorganisms, which composition consists essentially of an effective amount of a compound of formula I according to claim 1, together with a suitable carrier.
 6. A method of controlling phytopathogenic microorganisms or of protecting cultivated plants from attack by said microorganisms, which method comprises applying to said plants or to the locus thereof or to parts of plants a compound of formula I according to claim
 1. 7. A method according to claim 6, wherein the parts of plants are seeds. 